CN102163739B - Non-aqueous electrolyte secondary battery and method of manufacturing the same - Google Patents

Non-aqueous electrolyte secondary battery and method of manufacturing the same Download PDF

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Publication number
CN102163739B
CN102163739B CN201110039007.0A CN201110039007A CN102163739B CN 102163739 B CN102163739 B CN 102163739B CN 201110039007 A CN201110039007 A CN 201110039007A CN 102163739 B CN102163739 B CN 102163739B
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lighium thing
containing lighium
otide containing
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active material
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CN102163739A (en
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齐藤元治
藤本正久
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Panasonic New Energy Co ltd
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Sanyo Electric Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

A non-aqueous electrolyte secondary battery has a positive electrode containing a positive electrode active material, a negative electrode, and a non-aqueous electrolyte. The positive electrode active material includes a lithium-containing oxide obtained by ion exchanging a portion of sodium contained in a cobalt-containing oxide with lithium, the cobalt-containing oxide represented by the formula Lix1Nay1Co[alpha]Mn[beta]MzO[gamma] where: M is at least one element selected from the group consisting of Mg, Ni, Zr, Mo, W, Al, Cr, V, Ce, Ti, Fe, K, Ca, and In; 0<x1<0.45; 0.66<y1<0.75; 0.62<=[alpha]<=0.72; 0.28<=[beta]<=0.38; 0<=z<=0.1; and 1.9<=[gamma]<=2.1.

Description

Rechargeable nonaqueous electrolytic battery and manufacture method thereof
Technical field
The present invention relates to rechargeable nonaqueous electrolytic battery and manufacture method thereof.
Background technology
At present, rechargeable nonaqueous electrolytic battery is widely used as having the secondary cell of high-energy-density.
All the time, as the positive electrode of rechargeable nonaqueous electrolytic battery, for example, use LiCoO 2deng lithium-transition metal composite oxide etc.As negative material, for example, use and can inhale material with carbon element that seasoning goes out lithium etc.As nonaqueous electrolytic solution, use in the organic solvents such as ethylene carbonate (ethylene carbonate), diethyl carbonate (dimethyl carbonate) and dissolve as electrolytical LiBF 4, LiPF 6deng lithium salts and the material obtaining.
In recent years, along with being increased by the power consumption that uses the multifunction etc. of portable set of rechargeable nonaqueous electrolytic battery to cause, strongly expect the rechargeable nonaqueous electrolytic battery that energy density is higher.
In order to realize the rechargeable nonaqueous electrolytic battery with high-energy-density, need to make positive active material high capacity.Therefore, for example in following patent documentation 1,2 and non-patent literature 1～3 etc., various positive active material and the manufacture methods thereof with high power capacity have been proposed.
But, be widely used as positive active material at present containing lithium lamellar compound LiCoO 2crystal structure be the O3 structure that belongs to space group R-3m.Contain lithium lamellar compound LiCoO for this 2if be 4.5V (vs.Li/Li by making current potential +) seize above the lithium of 50% left and right in crystal structure, crystal structure meeting avalanche, has invertibity and reduces tendency.Therefore, using LiCoO 2containing in the situation of lithium lamellar compound of such O3 structure, the maximum specific discharge capacity that can realize is 160mAh/g left and right.
In order further to improve specific discharge capacity, be the structure that also can keep rock-steady structure in the time that more lithium is captured even if need to make the structure of positive active material.There is the method containing lithium lamellar compound of such structure as manufacture, proposed by manufacturing the method containing lithium lamellar compound to carrying out ion-exchange containing sodium lamellar compound.
Particularly, for example in following patent documentation 1, recorded the method for making the otide containing lighium thing that comprises sodium by making a part of sodium contained containing na oxide and lithium carry out ion-exchange.In addition, as the otide containing lighium thing of making by the method, recorded and belonged to space group P6 3mc and/or space group Cmca, with chemical constitution formula Li ana bmn xco yo 2 ± αthe otide containing lighium thing that (0.5≤A≤1.2,0 < B≤0.01,0.40≤x≤0.55,0.40≤y≤0.55,0.80≤x+y≤1.10, and 0≤α≤0.3) represent.
Even if the otide containing lighium thing of recording in this patent documentation 1 is taken away a large amount of lithiums because charging to high potential, its crystal structure is also not easy avalanche.Therefore, in patent documentation 1, recorded by using this otide containing lighium thing can obtain the main idea of high charge-discharge specific capacity as positive active material.
prior art document
patent documentation
Patent documentation 1: TOHKEMY 2009-32681 communique
Patent documentation 2: TOHKEMY 2002-220231 communique
non-patent literature
Non-patent literature 1:J.Electrochem.Soc, 149 (8) (2002) A1083
Non-patent literature 2:J.Electrochem.Soc, 147 (7) (2000) 2478
Non-patent literature 3:Solid State Ionics 144 (2001) 263
Summary of the invention
the problem that invention will solve
But, do not make it maximize in order to make rechargeable nonaqueous electrolytic battery high capacity, importantly, not only the discharge capacity of Unit Weight wants high, and the discharge capacity of per unit volume also wants high.In order to increase the discharge capacity of per unit volume, need to increase the real density of positive active material.That is, do not make it maximize in order to make rechargeable nonaqueous electrolytic battery high capacity, need the large and high positive active material of real density of the discharge capacity of per unit weight.
But, for the positive active material being formed by the otide containing lighium thing forming with record in above-mentioned patent documentation 1, be difficult to make its real density fully to increase.The real density of the positive active material of in fact, recording in patent documentation 1 is 4.44g/cm 3, far below the LiCoO of general utilized O3 structure 2real density, i.e. 5g/cm 3.
In addition, real density can be increased to 5.0g/cm although recorded it in patent documentation 1 3but what the inventor etc. furtherd investigate found that, in the positive active material that forms of otide containing lighium thing of recording in by patent documentation 1, manganese ratio in composition is high, cobalt ratio is low, therefore cannot fully improve its real density.More specifically find, manganese ratio in composition is high, cobalt ratio low, even in the time making a part of sodium contained containing cobalt/cobalt oxide and lithium carry out ion-exchange, also cannot significantly improve real density.
The present invention completes in view of described problem, and its object is, the rechargeable nonaqueous electrolytic battery of small-sized and high power capacity is provided.
for the scheme of dealing with problems
The first rechargeable nonaqueous electrolytic battery of the present invention relates to and possesses the positive pole that comprises positive active material and the rechargeable nonaqueous electrolytic battery of negative pole and nonaqueous electrolyte.Positive active material is formed by otide containing lighium thing, and described otide containing lighium thing is by making with Li x1na y1co αmn βm zo γ(M is at least one element selecting in the group of free Mg, Ni, Zr, Mo, W, Al, Cr, V, Ce, Ti, Fe, K, Ca and In composition.0 < x1 < 0.45,0.66 < y1 < 0.75,0.62≤α≤0.72,0.28≤β≤0.38,0≤z≤0.1,1.9≤γ≤2.1) represent carry out ion-exchange and obtain containing contained a part of sodium and the lithium of cobalt/cobalt oxide.
The manufacture method of rechargeable nonaqueous electrolytic battery of the present invention relates to the manufacture method of the rechargeable nonaqueous electrolytic battery that possesses the positive pole that comprises positive active material and negative pole and nonaqueous electrolyte.The manufacture method of rechargeable nonaqueous electrolytic battery of the present invention is by making with Li x1na y1co αmn βm zo γ(M is at least one element selecting in the group of free Mg, Ni, Zr, Mo, W, Al, Cr, V, Ce, Ti, Fe, K, Ca and In composition.0 < x1 < 0.45,0.66 < y1 < 0.75,0.62≤α≤0.72,0.28≤β≤0.38,0≤z≤0.1,1.9≤γ≤2.1) represent carry out ion-exchange containing the contained a part of sodium of cobalt/cobalt oxide and lithium and make positive active material.
In the present invention, preferably, positive active material is with Li x2na y2co αmn βm zo γ(M is at least one element selecting in the group of free Mg, Ni, Zr, Mo, W, Al, Cr, V, Ce, Ti, Fe, K, Ca and In composition.0.66 < x2 < 1,0 < y2≤0.01,0.62≤α≤0.72,0.28≤β≤0.38,0≤z≤0.1,1.9≤γ≤2.1) the otide containing lighium thing that represents.
In the present invention, be to make by making a part of sodium contained containing cobalt/cobalt oxide and lithium carry out ion-exchange as the otide containing lighium thing of positive active material.Therefore,, even be taken away a large amount of lithiums because charging to high potential, the crystal structure of otide containing lighium thing is also not easy avalanche.Therefore, can realize the high discharge capacity of per unit weight.
And then, for make as the otide containing lighium thing of positive active material containing cobalt/cobalt oxide, manganese ratio is low, cobalt ratio is high.Therefore,, by making to carry out ion-exchange containing contained a part of sodium and the lithium of cobalt/cobalt oxide, can obtain high real density.
As mentioned above, in the present invention, positive pole comprises the positive active material being formed by otide containing lighium thing, and the discharge capacity of the per unit weight of described otide containing lighium thing is high and real density is high.Therefore, can realize small-sized and there is the rechargeable nonaqueous electrolytic battery of high power capacity.
In addition, in the present invention, comprise Li for what make otide containing lighium thing containing cobalt/cobalt oxide, not comprising Li containing in cobalt/cobalt oxide, when x1=0, cannot obtain high real density.As the cobalt/cobalt oxide that contains for making otide containing lighium thing, the cobalt/cobalt oxide that contains that contains Li by use, can realize high real density.But when too much containing the contained Li of cobalt/cobalt oxide, the ratio of the Li importing by ion-exchange in the contained Li of otide containing lighium thing can reduce.Therefore, the specific capacity of the per unit volume of positive active material can reduce.Therefore, x1 is 0 < x1 < 0.45.
In the present invention, when very few containing the contained Na of cobalt/cobalt oxide, the ratio of the Li importing by ion-exchange in the contained Li of otide containing lighium thing can reduce.Therefore, the specific capacity of the per unit volume of positive active material reduces.On the other hand, when too much containing the contained Na of cobalt/cobalt oxide, moisture absorption is high, is difficult to synthesize.Therefore, y1 is 0.66 < y1 < 0.75.
In the present invention, in the time that, Mn few containing the contained Co of cobalt/cobalt oxide is many, even carry out ion-exchange containing contained a part of sodium and the lithium of cobalt/cobalt oxide in the case of making, also cannot significantly improve real density.,, in order significantly to increase real density by making to carry out ion-exchange containing the contained a part of sodium of cobalt/cobalt oxide and lithium, need to make to contain that the contained Co of cobalt/cobalt oxide is many, Mn is few.But, when, Mn too much containing the Co that cobalt/cobalt oxide is contained is few, can in the time of ion-exchange, include impurity.Therefore, α is in 0.67 ± 0.05 scope (0.62≤α≤0.72).β is in 0.33 ± 0.05 scope (0.28≤β≤0.38).Thus, can obtain the otide containing lighium thing that real density is high.
In the present invention, containing at least one element M that can comprise in cobalt/cobalt oxide in the group of selecting free Mg, Ni, Zr, Mo, W, Al, Cr, V, Ce, Ti, Fe, K, Ca and In composition.By adding element M, the thermal stability can improve charging time.But when too much containing the content of the M in cobalt/cobalt oxide, average discharge potential can reduce or real density can step-down, therefore can damage the advantage as high power capacity positive active material.Therefore, 0≤z≤0.1.
In the present invention, containing the contained hyperoxia of cobalt/cobalt oxide or when very few, have the stable problem of crystal structure that cannot keep containing cobalt/cobalt oxide.Therefore, γ is in 2 ± 0.1 scope.
In the first rechargeable nonaqueous electrolytic battery of the present invention, more preferably 4.8g/cm of the real density of positive active material 3above, 5.0g/cm more preferably 3above.Wherein, although the real density of positive active material is more high better, consider that the boundary of the Nomenclature Composition and Structure of Complexes is 5.1g/cm 3left and right.Therefore, the real density of positive active material is preferably 5.1g/cm 3below.
The second rechargeable nonaqueous electrolytic battery of the present invention relates to and possesses the positive pole that comprises positive active material and the rechargeable nonaqueous electrolytic battery of negative pole and nonaqueous electrolyte.In the second rechargeable nonaqueous electrolytic battery of the present invention, positive active material is by with Li x2na y2co αmn βm zo γ(M is at least one element selecting in the group of free Mg, Ni, Zr, Mo, W, Al, Cr, V, Ce, Ti, Fe, K, Ca and In composition.0.66 < x2 < 1,0 < y2≤0.01,0.62≤α≤0.72,0.28≤β≤0.38,0≤z≤0.1,1.9≤γ≤2.1) represent and real density is 4.8g/cm 3above otide containing lighium thing forms.
Make and obtain by making a part of sodium contained containing cobalt/cobalt oxide and lithium carry out ion-exchange as the otide containing lighium thing of the positive active material in the second rechargeable nonaqueous electrolytic battery of the present invention.Therefore,, even if can make otide containing lighium thing be taken away a large amount of lithiums because charging to high potential, crystal structure is also not easy avalanche.Thereby, can realize the high discharge capacity of per unit weight.
In addition, the real density of positive active material is 4.8g/cm 3above, higher.Therefore, can realize small-sized and there is the rechargeable nonaqueous electrolytic battery of high power capacity.
In the present invention, when very few as the content of the Li in the otide containing lighium thing of positive active material, the lithium that can participate in discharging and recharging can tail off, thereby theoretical capacity can reduce.In addition, when the content of the Li in otide containing lighium thing is too much, lithium can enter transition metal site, and this also can cause theoretical capacity to reduce.Therefore, as lithium amount, preferably 0.66 < x2 < 1.
When the content of Na in otide containing lighium thing is too much, sometimes because insertion and the disengaging of sodium cause structural deterioration.Therefore, 0 < y2≤0.01.In addition, y2≤0.01 o'clock, XRD determining is sometimes examined and is not measured Na.
When the content content few, Mn of Co in otide containing lighium thing is many, cannot obtain sufficiently high real density.In order to obtain sufficiently high real density, need to make the content of the Co in otide containing lighium thing many, the content of Mn is few.But the content of the Co in otide containing lighium thing too much, the content of Mn is when very few, at 4.6V (vs.Li/Li +) can see that it shifts to the structure that cannot obtain stable characteristic in above charging process.Therefore, α is in 0.67 ± 0.05 scope.β is in 0.33 ± 0.05 scope.
In the present invention, in otide containing lighium thing, can comprise at least one element M in the group of selecting free Mg, Ni, Zr, Mo, W, Al, Cr, V, Ce, Ti, Fe, K, Ca and In composition.By adding element M, the thermal stability can improve charging time.But when the content of M is too much, average discharge potential can reduce or real density can step-down, can damage the advantage as high power capacity positive active material.Therefore, 0≤z≤0.1.
The hyperoxia that otide containing lighium thing is contained or when very few, existence cannot keep the stable problem of crystal structure.Therefore, γ is in 2 ± 0.1 scope.
In the second rechargeable nonaqueous electrolytic battery of the present invention, the real density of positive active material is less than 4.8g/cm 3time, be difficult to fully improve the discharge capacity of per unit volume.More preferably 4.8g/cm of the real density of positive active material 3above, 5.0g/cm more preferably 3above.Wherein, although the real density of positive active material is more high better, consider that the boundary of the Nomenclature Composition and Structure of Complexes is 5.1g/cm 3left and right.Therefore, the real density of positive active material is preferably 5.1g/cm 3below.
In the present invention, otide containing lighium thing preferably comprises: belong to space group P6 3the otide containing lighium thing of the O2 structure of mc and belong at least one class otide containing lighium thing in the otide containing lighium thing of T2 structure of space group Cmca; And belong to the otide containing lighium thing of space group C2/m or C2/c.By being this formation, can further improve the stability at the crystal structure of positive active material when charging to high potential and be taken away a large amount of lithiums.Therefore, can realize the higher discharge capacity of per unit weight.More preferably, otide containing lighium thing preferably comprises and belongs to space group P6 3the otide containing lighium thing of the O2 structure of mc and belong to space group Cmca T2 structure otide containing lighium thing and belong to otide containing lighium thing whole of space group C2/m or C2/c.
In addition, " O2 structure " refers to following structure: lithium is present in the center of oxygen octahedra, and on average has the overlapping of two kinds of oxygen and transition metal in structure cell.
" O3 structure " refers to following structure: lithium is present in the center of oxygen octahedra, and on average has the overlapping of three kinds of oxygen and transition metal in structure cell.As belonging to space group P6 3the otide containing lighium thing of the O2 structure of mc, the general known LiCoO that has 2deng.
" T2 structure " refers to following structure: lithium is present in the center of oxygen tetrahedral structure, and on average has the overlapping of two kinds of oxygen and transition metal in structure cell.As the otide containing lighium thing of T2 structure that belongs to space group Cmca, general known have a Li 2/3co 2/3mn 1/3o 2, Li 0.7ni 1/3mn 2/3o 2deng.
As the representational otide containing lighium thing that belongs to space group C2/m or C2/c, the general known Li that has 2mnO 3, by Li 2mnO 3in the part of manganese obtain with other metal replacements as Li 2mn 1-xm xo 3, Li 1.2mn 0.54ni 0.13co 0.13o 2such stratiform rock salt structure and Li 2mnO 3solid solution.
In addition, at least one class otide containing lighium thing in the otide containing lighium thing of the otide containing lighium thing to O2 structure and T2 structure, be not particularly limited with the form that exists of otide containing lighium thing that belongs to space group C2/m or C2/c.Be that otide containing lighium thing can be at least one class otide containing lighium thing in the otide containing lighium thing of O2 structure and the otide containing lighium thing of T2 structure and solid solution or the mixture that belongs to the otide containing lighium thing of space group C2/m or C2/c.
Otide containing lighium thing comprises and belongs to space group P6 3when the otide containing lighium thing of the O2 structure of mc, belong to space group P6 3the lattice constant a of the otide containing lighium thing of the O2 structure of mc preferably exists above and be less than scope in, lattice constant c preferably exists above and be less than scope in.Now, form Stability Analysis of Structures and there is the high power capacity positive active material of high real density.
When otide containing lighium thing that otide containing lighium thing comprises the T2 structure that belongs to space group Cmca, preferably, the lattice constant a that belongs to the otide containing lighium thing of the T2 structure of space group Cmca exists above and be less than scope in, lattice constant b exists above and be less than scope in, and lattice constant c exists above and be less than scope in.Now, even if form the high power capacity positive active material that seizes a large amount of lithium structures and also stablize, have high real density from structure.
In the present invention, as long as the anodal positive active material that comprises the invention described above is not particularly limited.The anodal lip-deep anode mixture layer that for example can have the collector body being formed by the conductive foil such as metal forming, Alloy Foil and be formed on this collector body, this anode mixture layer can comprise the positive active material of the invention described above.In addition, in anode mixture layer, on the basis of the positive active material of the invention described above, can also comprise the other materials such as adhesive, conductive agent.
As the adhesive adding, can list polytetrafluoroethylene, polyvinylidene fluoride, poly(ethylene oxide), polyvinyl acetate, polymethacrylates, polyacrylate, polyacrylonitrile, polyvinyl alcohol, butadiene-styrene rubber, carboxymethyl cellulose in anode mixture layer.These adhesives can use separately, also can combine multiple use.
When the content of the adhesive in anode mixture layer is many, the content of the positive active material in anode mixture layer can be too small sometimes, can not get high-energy-density.Therefore, more than the content of the adhesive in anode mixture layer is preferably 0 quality % and below 30 quality %, more preferably more than 0 quality % and below 20 quality %, more preferably more than 0 quality % and below 10 quality %.
When the conductance of positive active material is high, might not in anode mixture layer, add conductive agent.On the other hand, when the conductance of positive active material is low, preferably in anode mixture layer, add conductive agent.As the conductive agent adding, can list electroconductive oxide, conductive carbide, conductive nitride etc. in anode mixture layer.As the object lesson of electroconductive oxide, can list tin oxide, indium oxide etc.As conductive carbide, can list tungsten carbide, zirconium carbide etc.As conductive nitride, can list titanium nitride, tantalum nitride etc.
The in the situation that of adding conductive agent in anode mixture layer, when the addition of conductive agent is very few, cannot fully improve sometimes the conductivity of anode mixture layer, on the other hand, when the addition of conductive agent is too much, sometimes the content of the positive active material in anode mixture layer can be very few, cannot obtain high-energy-density.Therefore, more than the content of the conductive agent in anode mixture layer is preferably 0 quality % and below 30 quality %, more preferably more than 0 quality % and below 20 quality %, more preferably more than 0 quality % and below 10 quality %.
In the present invention, negative pole is not particularly limited.Silicon materials that negative pole for example can be by lithium, silicon, carbon, tin, germanium, aluminium, lead, indium, gallium, lithium alloys, silicon alloy, inhale the material with carbon element of contain lithium in advance, inhale contain lithium in advance etc. form.
In the present invention, nonaqueous electrolyte is also not particularly limited.As the solvent of nonaqueous electrolyte, can list cyclic carbonate, linear carbonate, ester class, ring-type ethers, chain ethers, nitrile, amide-type etc.As the object lesson of cyclic carbonate, can list ethylene carbonate, propylene carbonate, butylene carbonate etc.Also can use part or all material being fluorinated of hydrogen base of these cyclic carbonates as the solvent of nonaqueous electrolyte.As the object lesson of part or all material being fluorinated of the hydrogen base of cyclic carbonate, can list the sub-propyl ester of carbonic acid trifluoro (trifluoropropylene carbonate), carbonic acid fluoroethylene (fluoroethylenecarbonate) etc.As the object lesson of linear carbonate, can list dimethyl carbonate, carbonic acid ethyl methyl esters, diethyl carbonate, carbonic acid methyl propyl ester, carbonic acid ethyl propyl ester, carbonic acid methyl isopropyl ester etc.Also can use part or all material being fluorinated of hydrogen base of these linear carbonate as the solvent of nonaqueous electrolyte.As the object lesson of ester class, can list methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton etc.As the object lesson of ring-type ethers, can list 1,3-dioxolanes, 4-methyl isophthalic acid, 3-dioxolanes, oxolane, 2-methyltetrahydrofuran, expoxy propane, 1,2-epoxy butane, Isosorbide-5-Nitrae-dioxs, 1,3,5-trioxane, furans, 2-methylfuran, 1,8-cineole, crown ether etc.As the object lesson of chain ethers, can list 1, 2-dimethoxy-ethane, diethyl ether, dipropyl ether, diisopropyl ether, butyl oxide, two hexyl ethers, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethylphenyl ether, butyl phenylate, amyl group phenyl ether, methoxy toluene, benzylisoeugenol, diphenyl ether, benzyl ether, o-dimethoxybenzene, 1, 2-diethoxyethane, 1, 2-dibutoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, 1, 1-dimethoxymethane, 1, 1-diethoxyethane, TRIGLYME, tetraethyleneglycol dimethyl ether etc.As the object lesson of nitrile, can enumerate acetonitrile etc.As the object lesson of amide-type, can enumerate dimethyl formamide etc.Also can use material that multiple above-mentioned solvent the is formed solvent as nonaqueous electrolyte.
As the lithium salts adding, for example, can list LiBF in nonaqueous electrolyte 4, LiPF 6, LiCF 3sO 3, LiC 4f 9sO 3, LiN (CF 3sO 2) 2, LiN (C 2f 5sO 2) 2, LiAsF 6, difluoro (oxalate) lithium borate, their two or more mixture.
the effect of invention
According to the present invention, can provide the rechargeable nonaqueous electrolytic battery of small-sized and high power capacity.
Brief description of the drawings
Fig. 1 is the chart that the XRD determining result containing cobalt/cobalt oxide in embodiment 1 is shown.
Fig. 2 is the chart that the XRD determining result of the otide containing lighium thing in embodiment 1 is shown.
Fig. 3 is the constructed profile of the test cell of making in embodiment 1.
Fig. 4 is the chart that the charging and discharging curve of the test cell of making in embodiment 1 is shown.
Fig. 5 is the chart that the XRD determining result of the otide containing lighium thing in embodiment 1～3 and comparative example 1,2 is shown.
description of reference numerals
1 ... anodal
2 ... negative pole
3 ... reference electrode
4 ... barrier film
5 ... lead-in wire
6 ... lamination vessel
7 ... nonaqueous electrolyte
8 ... test cell
Embodiment
Further describe the present invention, but the present invention is not limited to following embodiment completely, can in the scope that does not change its main idea, suitably change and implement below.
embodiment 1
First, use sodium nitrate (NaNO 3), lithium carbonate (Li 2cO 3), cobalt oxide (II III) (Co 3o 4), manganese oxide (III) (Mn 2o 3), make with Li 0.1na 0.7co 0.67mn 0.33o 2represent containing cobalt/cobalt oxide.Particularly, measure respectively above-mentioned initiation material to reach target ratio of components, they are fully mixed.This mixture is put into stove, at 900 DEG C, kept 10 hours, make thus above-mentioned containing cobalt/cobalt oxide.
XRD determining result and the Na containing cobalt/cobalt oxide of made 0.74coO 2and Li (PDF#87-0274) 2mnO 3(PDF#73-0152) XRD determining the results are shown in Fig. 1.In addition, in the present embodiment, use CuK αas the radiation source of XRD determining.
Then, containing cobalt/cobalt oxide, utilize the lithium nitrate (LiNO of 88mol% for above-mentioned 3) with the bed of molten salt that the lithium chloride (LiCl) of 12mol% mixes, make, carrying out ion-exchange containing contained a part of sodium and the lithium of cobalt/cobalt oxide, to make thus with Li 0.77na 0.001co 0.67mn 0.33o 2the otide containing lighium thing representing.
Particularly, first, weigh 5g just in time with Li 0.1na 0.7co 0.66mn 0.34o 2represent containing cobalt/cobalt oxide, this bed of molten salt containing 5 times of equivalents of cobalt/cobalt oxide is added containing in cobalt/cobalt oxide, at 280 DEG C, keep 10 hours.Thereafter, washing solid constituent, makes it dry, makes thus with Li 0.77na 0.001co 0.67mn 0.33o 2the otide containing lighium thing representing.XRD determining result and the Li of the otide containing lighium thing of made 0.73coO 2and Li (PDF#37-1162) 2mnO 3(PDF#73-0152) XRD determining the results are shown in Fig. 2.
In addition, measure the real density of gained otide containing lighium thing with the dry type densitometry of the constant volume plavini based on helium.
Then, use this otide containing lighium thing as positive active material, make anodal.Particularly, using the otide containing lighium thing of 80 quality %, mix as the acetylene black of 10 quality % of conductive agent with as the polyvinylidene fluoride of 10 quality % of binding agent, come slurried with METHYLPYRROLIDONE.Gained slurries are coated on aluminium foil, and vacuumize at 110 DEG C, forms, and makes thus anodal.
Then, make negative pole by the size that lithium metal is cut into regulation.In addition, make reference electrode by the size that lithium metal is cut into regulation.
Then, use positive pole 1, negative pole 2, reference electrode 3, the barrier film 4 being formed by polyethylene, lead-in wire 5, lamination vessel 6 and the nonaqueous electrolyte 7 of above-mentioned making, in inert atmosphere, the test cell 8 of structure shown in construction drawing 3.In addition, as nonaqueous electrolyte 7, use the material that obtains as follows: in the electrolyte that the ratio mixed carbonic acid ethyl with 30: 70 volume % and carbonic acid two ethyls form, add phosphorus hexafluoride acid lithium (LiPF 6) to make its concentration be 1.0mol/l.
Current density is set as to 0.1mA/cm 3, at 2.0V-5.0V (vs.Li/Li +) scope gained test cell 8 is discharged and recharged, discharge and recharge thus test.Fig. 4 illustrates the charging and discharging curve of the test cell of the present embodiment.
embodiment 2
Except using with Li 0.2na 0.7co 0.67mn 0.33o 2what represent contains beyond cobalt/cobalt oxide, similarly makes otide containing lighium thing with above-described embodiment 1, and makes test cell, the charge-discharge characteristic of evaluation test battery.
embodiment 3
Except using with Li 0.3na 0.7co 0.67mn 0.33o 2what represent contains beyond cobalt/cobalt oxide, similarly makes otide containing lighium thing with above-described embodiment 1, and makes test cell, the charge-discharge characteristic of evaluation test battery.
comparative example 1
Except use do not comprise Li with Na 0.7co 0.67mn 0.33o 2what represent contains beyond cobalt/cobalt oxide, similarly makes otide containing lighium thing with above-described embodiment 1, and makes test cell, the charge-discharge characteristic of evaluation test battery.
comparative example 2
Except using with Li 0.4na 0.7co 0.67mn 0.33o 2what represent contains beyond cobalt/cobalt oxide, similarly makes otide containing lighium thing with above-described embodiment 1, and makes test cell, the charge-discharge characteristic of evaluation test battery.
Fig. 5 illustrates XRD determining result and the LiCoO of the otide containing lighium thing in embodiment 1～3 and comparative example 1,2 in the lump 2and Li (PDF#70-2685) 2mnO 3(PDF#73-0152) XRD determining result.
As shown in Figure 5, the XRD profile of the otide containing lighium thing of comparative example 1 and the XRD profile of T2 structure are basically identical.Hence one can see that, and the otide containing lighium thing of comparative example 1 is made up of the otide containing lighium thing of T2 structure.
The XRD profile of the otide containing lighium thing of comparative example 2 is to be mixed by the XRD profile of O2 structure and the XRD profile that belongs to the material of space group C2/m or C2/c.Hence one can see that, the otide containing lighium thing that comprises O2 structure in the otide containing lighium thing of comparative example 2 and the otide containing lighium thing that belongs to space group C2/m or C2/c.
In any one of embodiment 1～3, the XRD profile of otide containing lighium thing is to be mixed by the XRD profile of T2 structure and the XRD profile of O2 structure and the XRD profile that belongs to the material of space group C2/m or C2/c.But, the approximation of the XRD profile of the otide containing lighium thing of embodiment 1 and the XRD profile of T2 structure is the strongest, the approximation of the XRD profile of the otide containing lighium thing of embodiment 3 and the XRD profile of O2 structure is the strongest, and the XRD profile of the otide containing lighium thing of embodiment 2 is positioned at their centre.From these, the otide containing lighium thing that each otide containing lighium thing in embodiment 1～3 comprises T2 structure and the otide containing lighium thing of O2 structure and belong to the otide containing lighium thing of space group C2/m or C2/c.Known, for the containing ratio of the otide containing lighium thing of T2 structure, embodiment 1 is the highest, and embodiment 3 is minimum.Known, for the containing ratio of the otide containing lighium thing of O2 structure, embodiment 3 is the highest, and embodiment 1 is minimum.
In following table 1, gather the ratio of components (containing cobalt/cobalt oxide, otide containing lighium thing) that feeds intake composition and obtained by the results of elemental analyses of the sample of actual fabrication of each embodiment and comparative example.For ratio of components, obtain lithium, sodium by atom luminesceence analysis, obtain manganese, cobalt by ICP luminesceence analysis.In table 1, taking cobalt and manganese and as 1, each ratio of components is shown taking oxygen as 2.In addition, structure and real density and the initial discharge specific capacity of the oxide contained at the otide containing lighium thing of each embodiment and comparative example in following table 2, have been gathered.
[table 1]
Composition feeds intake Containing cobalt/cobalt oxide Otide containing lighium thing
Embodiment 1 Li 0.1Na 0.7Co 0.67Mn 0.33O 2 Li 0.10Na 0.70Co 0.66Mn 0.34O 2 Li 0.77Na 0.001Co 0.67Mn 0.33O 2
Embodiment 2 Li 0.2Na 0.7Co 0.67Mn 0.33O 2 Li 0.20Na 0.70Co 0.88Mn 0.34O 2 Li 0.85Na 0.001Co 0.67Mn 0.33O 2
Embodiment 3 Li 0.3Na 0.7Co 0.67Mn 0.33O 2 Li 0.31Na 0.70Co 0.86Mn 0.34O 2 Li 0.9Na 0.002Co 0.67Mn 0.33O 2
Comparative example 1 Na 0.7Co 0.67Mn 0.33O 2 Na 0.72Co 0.86Mn 0.34O 2 Li 0.71Na 0.001Co 0.66Mn 0.34O 2
Comparative example 2 Li 0.4Na 0.7Co 0.67Mn 0.33O 2 Li 0.41Na 0.69Co 0.66Mn 0.34O 2 Li 0.94Na 0.002Co 0.67Mn 0.33O 2
[table 2]
As shown in Table 1 above, in the two, more than the initial discharge specific capacity of per unit weight is 220mAh/g, higher at embodiment 1～3 and comparative example 1,2.Can think that its reason is as follows: as shown in table 2, in any one of embodiment 1～3 and comparative example 1,2, the otide containing lighium thing that otide containing lighium thing comprises the T2 structure that belongs to space group Cmca and belong to space group P6 3at least one class in the otide containing lighium thing of the O2 structure of mc, even in the time being charged to high potential, being captured a large amount of lithiums, the crystal structure of otide containing lighium thing is also not easy avalanche.
But in comparative example 1,2, real density is 4.7g/cm 3below, lower, therefore the initial discharge specific capacity of per unit volume is below 1050Ah/L, also lower.On the other hand, in embodiment 1～3, real density is 4.8g/cm 3above, higher, therefore the initial discharge specific capacity of per unit volume is more than 1060Ah/L, also higher.
From the above results, use the cobalt/cobalt oxide that contains according to composition of the present invention, and make the otide containing lighium thing that carries out ion-exchange containing the contained a part of sodium of cobalt/cobalt oxide and lithium as positive active material, can make rechargeable nonaqueous electrolytic battery high capacity thus and do not maximize.
In addition, in the comparative example 1 that does not contain Li, only can obtain 4.66g/cm containing cobalt/cobalt oxide 3low like this real density, hence one can see that, in order to obtain high real density, need to contain Li containing cobalt/cobalt oxide.
In addition, in comparative example 2, although contain Li containing cobalt/cobalt oxide, be that Li (x2) more than 1 and in otide containing lighium thing is more than 1 containing the summation (x1+y1) of the Li in cobalt/cobalt oxide and Na, also only can obtain 4.52g/cm 3low like this real density.Hence one can see that, in order to obtain high real density, need to make to be less than 1 and make the Li (x2) in otide containing lighium thing be less than 1 containing the summation (x1+y1) of the Li in cobalt/cobalt oxide and Na.
And then comparing embodiment 1～3 and comparative example 2 are known, larger containing the less real density of content (x1) of the Li in cobalt/cobalt oxide, the initial discharge specific capacity of per unit volume is also larger.Can think that its reason is as follows: the content (x1) hour of Li, in otide containing lighium thing, the ratio regular meeting that contains the Li of the contained Li origin of cobalt/cobalt oxide tails off, it is many that the ratio of the Li importing by ion-exchange becomes, and therefore the crystal structure of otide containing lighium thing can form firm crystal structure by seizing of lithium.Therefore, content (x1) containing the Li in cobalt/cobalt oxide is preferably below 0.35 with respect to the ratio (x1/ (x1+y1)) of the summation (x1+y1) of the content of the Na containing in cobalt/cobalt oxide and Li, more preferably below 0.3, more preferably, below 0.25, be further preferably below 0.23.
Following table 3 illustrate embodiment 1～3 and comparative example 1,2, by T2 structure or the definite lattice constant of O2 structure.
[table 3]
Result is as shown in Table 3 known, it is desirable to, and belongs to P6 3the lattice constant a of the otide containing lighium thing of the O2 structure of mc exists above and be less than scope in, and lattice constant c exists above and be less than scope in.In lattice constant, a is less than lattice constant c is less than material in, the Stability Analysis of Structures that contains lithium, therefore seizing of lithium can make structure easily become unstable.Thereby, cannot capture a large amount of lithiums, specific capacity is little.On the other hand, lattice constant a is above, lattice constant c is the real density of above material is little.
It is desirable to, the lattice constant a that belongs to the otide containing lighium thing of the T2 structure of Cmca exists above and be less than scope in, lattice constant b exists above and be less than scope in, lattice constant c exists above and be less than scope in.
Be less than for lattice constant a scope or above scope, lattice constant c are being less than scope or the material of above scope, its structural instability, therefore can not get high specific capacity, and cycle characteristics is also bad.In addition, lattice constant b is being less than scope or when above scope, real density is little.
comparative example 3
Except using, the content of Co is many, Mn poor with Na 0.7co 0.83mn 0.17o 2what represent contains beyond cobalt/cobalt oxide, similarly makes otide containing lighium thing with above-mentioned comparative example 1, and makes test cell, the charge-discharge characteristic of evaluation test battery.
But, in this comparative example, utilize the lithium nitrate (LiNO of 61mol% 3) and 39mol% lithium hydroxide (LiOHH 2o) material mixing is as bed of molten salt.For this bed of molten salt, 5g is added in the bed of molten salt containing 5 times of equivalents of cobalt/cobalt oxide containing cobalt/cobalt oxide, at 200 DEG C, keep 10 hours.
comparative example 4
Except use comprise Li with Li 0.1na 0.7co 0.83mn 0.17o 2what represent contains beyond cobalt/cobalt oxide, similarly makes otide containing lighium thing with above-mentioned comparative example 2, and makes test cell, the charge-discharge characteristic of evaluation test battery.
The chemical constitution formula containing cobalt/cobalt oxide and otide containing lighium thing of above-mentioned comparative example 3,4 and chemical constitution formula and the real density containing cobalt/cobalt oxide and otide containing lighium thing of real density and embodiment 1 and comparative example 1 are shown in following table 4 in the lump.
[table 4]
The embodiment 1 that relatively content of Co content few, Mn is many is known with comparative example 1, by adding Li containing in cobalt/cobalt oxide, can significantly improve the real density of gained otide containing lighium thing.On the other hand, from comparative example 3,4 relatively, in the poor situation of, Mn many at the content of Co, even adding Li containing in cobalt/cobalt oxide, the real density of gained otide containing lighium thing is also equal extent.From this result, by containing this effect of adding Li in cobalt/cobalt oxide and can improve real density being the peculiar effect that content at the Co containing in cobalt/cobalt oxide and Mn obtains according to situation of the present invention.The lithium of comparative example 3 is as follows more than the reason of the inventory of sodium: Co contains ratio when high, and in the time of ion-exchange, cobalt can be reduced, and lithium can additionally be inserted.

Claims (9)

1. a rechargeable nonaqueous electrolytic battery, it possesses the positive pole and negative pole and the nonaqueous electrolyte that comprise positive active material,
Described positive active material is formed by otide containing lighium thing, and described otide containing lighium thing is by making with Li x1na y1co αmn βm zo γwhat represent carries out ion-exchange and obtains containing contained a part of sodium and the lithium of cobalt/cobalt oxide, in formula, M is at least one element selecting in the group of free Mg, Ni, Zr, Mo, W, Al, Cr, V, Ce, Ti, Fe, K, Ca and In composition, 0<x1<0.45,0.66<y1<0.75,0.62≤α≤0.72,0.28≤β≤0.38,0≤z≤0.1,1.9≤γ≤2.1
Described otide containing lighium thing is with Li x2na y2co αmn βm zo γrepresent, in formula, M is at least one element selecting in the group of free Mg, Ni, Zr, Mo, W, Al, Cr, V, Ce, Ti, Fe, K, Ca and In composition, 0.66<x2<1,0<y2≤0.01,0.62≤α≤0.72,0.28≤β≤0.38,0≤z≤0.1,1.9≤γ≤2.1.
2. rechargeable nonaqueous electrolytic battery according to claim 1, wherein, the real density of described positive active material is 4.8g/cm 3above.
3. a rechargeable nonaqueous electrolytic battery, it possesses the positive pole and negative pole and the nonaqueous electrolyte that comprise positive active material,
Described positive active material is by with Li x2na y2co αmn βm zo γexpression and real density are 4.8g/cm 3above otide containing lighium thing forms, in formula, M is at least one element selecting in the group of free Mg, Ni, Zr, Mo, W, Al, Cr, V, Ce, Ti, Fe, K, Ca and In composition, 0.66<x2<1,0<y2≤0.01,0.62≤α≤0.72,0.28≤β≤0.38,0≤z≤0.1,1.9≤γ≤2.1.
4. according to the rechargeable nonaqueous electrolytic battery described in claim 2 or 3, wherein, the real density of described positive active material is 5.1g/cm 3below.
5. according to the rechargeable nonaqueous electrolytic battery described in claim 1 or 3, wherein, described otide containing lighium thing comprises: belong to space group P6 3the otide containing lighium thing of the O2 structure of mc and belong at least one class otide containing lighium thing in the otide containing lighium thing of T2 structure of space group Cmca; And belong to the otide containing lighium thing of space group C2/m or C2/c.
6. rechargeable nonaqueous electrolytic battery according to claim 5, wherein, belongs to the otide containing lighium thing of the O2 structure of space group P63mc described in described otide containing lighium thing comprises,
The lattice constant a of the otide containing lighium thing of the described O2 structure that belongs to space group P63mc exists above and be less than scope in, lattice constant c exists above and be less than scope in.
7. rechargeable nonaqueous electrolytic battery according to claim 5, wherein, belongs to the otide containing lighium thing of the T2 structure of space group Cmca described in described otide containing lighium thing comprises,
The lattice constant a of the otide containing lighium thing of the described T2 structure that belongs to space group Cmca exists above and be less than scope in, lattice constant b exists above and be less than scope in, lattice constant c exists above and be less than scope in.
8. rechargeable nonaqueous electrolytic battery according to claim 5, wherein, described otide containing lighium thing belongs to space group P6 described in being 3the otide containing lighium thing of the O2 structure of mc and described in belong at least one class otide containing lighium thing in the otide containing lighium thing of T2 structure of space group Cmca with described in belong to solid solution or the mixture of the otide containing lighium thing of space group C2/m or C2/c.
9. a manufacture method for rechargeable nonaqueous electrolytic battery, described rechargeable nonaqueous electrolytic battery possesses the positive pole and negative pole and the nonaqueous electrolyte that comprise positive active material,
This manufacture method is by making with Li x1na y1co αmn βm zo γwhat represent carries out ion-exchange containing the contained a part of sodium of cobalt/cobalt oxide and lithium and makes described positive active material, in formula, M is at least one element selecting in the group of free Mg, Ni, Zr, Mo, W, Al, Cr, V, Ce, Ti, Fe, K, Ca and In composition, 0<x1<0.45,0.66<y1<0.75,0.62≤α≤0.72,0.28≤β≤0.38,0≤z≤0.1,1.9≤γ≤2.1
Positive active material is with Li x2na y2co αmn βm zo γthe otide containing lighium thing representing, in formula, M is at least one element selecting in the group of free Mg, Ni, Zr, Mo, W, Al, Cr, V, Ce, Ti, Fe, K, Ca and In composition, 0.66<x2<1,0<y2≤0.01,0.62≤α≤0.72,0.28≤β≤0.38,0≤z≤0.1,1.9≤γ≤2.1.
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